Purification of aminoacetonitrile by vacuum distillation



Aug. 12, 1947. 2,425,661 PURIFICATION OF mmoAcETom'rRILE BYvAcuUu DISTILLA'I'ION A. G." WEBER ET AL Filed Aug. 22'. 1944 INVENTOR)" NEQSE 33v QSSQ f MSEG Wber .Bell 0% V @NQQQEQQ Q n lzEllilzik l ilti Arthur G."

Patented Aug. 12, 1941 2,425,661

UNITED STATES PATENT opp- 5 smell-mos jfi msiomam a a: i

BY VACUUM DLXSIILLATION "Arthur woven: and chi-ewe n. neu, Wilmington, DeLflmi'gnors to lili I. du Pont deNemours ta Companm-Wilminzwn, Del., a corporation of Delaware 1 amine-sum; August 22, it, banal No. 550,531 7Glaims. tie-s "2) This invention relates to an improved method derived Irom" the amination oi Iormaldehyde for producing aminoaoetonitrile and more par- 'cyanhydrin. A further object is to provide a ticularly to the recovery of aminoacetonitrile from a process for preparing anhydrous aminoacetonl--- the crude reaction product obtained by'reacting trile. Other objects and adv ntages of theinformaldehyde cyanhydrinwith ammonia; vention will hereinafter appear. I

It is known that'aminoacetonitrile can be made The above objects are realized in accordwith by thev interaction of formaldehyde cyanhydrin i this invention by subjecting an aqueous solution (hydroxyacetonitrile) with ammonia. The am- 1 containing aminoacetonitrile, such as the crude monia is added to the cyanhydrin in an aqueous. 1 reaction product of the animation of formaldeor alcoholic solution and in accord/with the art 10' hyde cyanhydrin, to a series of'operations which it is stated that aminoacetonitrilemay be obtained involve heating the aqueous solution to vaporize in normal theoretical yield. No description has 1 the water and the major portion of the aminobeen found the art, however, describing how actonitrile, and substantiallyimmediatelytherethe aminoacetonitrile is recovered from the crude after separating the unvaporized liquids present reaction mixture, and while a reaction mixture from the vapors o1 aminoacetonitrile and water. may on analysis show theoretical yields, such a 'Thislcfl p bycontimlously subjecting showing has no real significance if the desired a stream lit the aqueous solution of aminoacetoproduct cannot be used because of the manycon- -..nitri1e to a heating step which rapidlyjvaporizes taminatingby-products produced with it which the water and most of the aminoacetonitrile,

cannot be separated satisfactorily from the crude f leaving the other constituents present in the reaction mixture. f liquid phase. Themixture of liquid and vapor Normally liquidcomponents. of liquid mixtures is passed from the heating step substantially can easily be separated we train of distillation "as rapidly as thevapor is formedinto a liquidcolumns if the boiling points of the constituents '"v'apor separator of the separation step, wherein present are as far apart as they are .in the crude the vapors aresubstantially completely separated product from the reaction of formaldehyde cyanfrom the liquids. If desired, the vapors may be hydrin and a'mmonia. s The crude "products from condensed, again heated and separated in a secthis reaction, however, cannot readily be so sep and series of operations similar to thefirst. The arated from the aminoacetonitrile because ofthe liquids and/or vapors separated in the first or unstable nature of the nitrile. If the crude prod- 3O isecond series of operations may be subsequently not is fed. directly to a vacuum distillation column, {treated in asimilar -manner to eifect completely the by-products together with the decomposition fij separation. l i products will soon plug the column and make it A principal feature of are invention involves inoperable. Furthermore; pure aminoacetonipassing a relatively small volume as, for example, trile, SilltahTflMOl hydrogenation has not hereto-l fastream of the liquid into a heater. wherein the fore been obtained principally because the low, iliquid is rapidly heated. This can be accomboiling decomposition products of the amino- "plishedby heating a portion of a tubethrough acetonitrile continuously form during the distilwhich the liquidis passing. As the aminoacetolation' and pass overhead to contaminate the aminitrile is vaporized, it increases the volume of the noacetonitrile product. The refining system-cle- 40 materials in the tube, and accordingly greatly scribed herein overcomes these diificulties. increases the flow through the tube. From the An object of the present invention is to pro heating tube the vapor-liquid mixture passes to a vide an improved process for the preparation of chamber in which the vapors and liquids are seppure aminoacetonitrile. A further objectq of the arated. Inasmuch as'amlnoacetonitrile decominvention is to provide a process for the recovery pos rapidly at elevated temperatures in both of aminoacetonitrile from the crude reaction the liquid and vapor phase and, moreover, as product obtainedby the interactionof formaldethe amount of aminoacetonitrile decomposing in hyde cyanhydrin with ammonia. Yet another the reflningsystem increases both as the time object is to provide a recovery process for sepof; heating is increased and as the boiling point of arating an aqueous solution-of amlnoacetonitrile the liquid in the heater is raised, the length of from solutions containing it as well as contami time required to vaporize the water and amino nating substances. A still further object is to acetonitrile should-be as short as possible and the provide amethcd whereby an aqueoussolution of yaporization shouldbe carried out at as low a aminoacetonitrile suitabletor hydrogenation can pressure aslpractical.

be separated from thecrude reaction product The processismorereadily visualized by refheater i, within which the mixture is heated sufiiciently to vaporize all of the water and most of the aminoacetonitrile. The resulting mixture of liquid and vapor passes tangentially into the separator 2, which is similar in construction to, a

cyclone separator, the liquid being discharged from the bottom, the vapors from thetop. Thevapors containing a substantial proportion of the aminoacetonitrile and water are liquified in the,

condenser 3, are passed on to a second heater 4 anda second separator 5, wherein the sameseries of processes effected in the first stage is carried out. The vapors from the second stage pass into the condenser 6, from which the liquid product is passed to storage. The liquid from separator 5 may, if desired, be returned as indicated in the drawing to the first stage to recover its aminoacetonitrile content, while the liquid from separator 2 is passed into a third stage illustrated by heater 1, wherein the liquid is also heated to ture, 0.75 part per third stage at a pressure of about 5 to about mm. and a temperature between about 55 and about 95 C. Adequate heating is provided by jacketing the heating zones with 2-15 pounds per square inch of steam or by other means giving an external temperature of about 110 C,

More specifically, the above process may be conducted, in the equipment described in the example, by introducing into the system as illustrated in the drawing 5.1 parts per hour of a crude reaction mixture obtained from the amination of formaldehyde cyanhydrin. To this mixhour of condensed vapors from the second stage of the reaction, e. g., from separator 5 are added, and the resulting composite mixture introduced into the heater I, wherein it is heated to a temperature between 65 and 85 e at substantially the same vaporize the aminoacetonitrile, and the liquid and vapors separated in separator 8. Prior to being introduced into this stage, water is added before heating in order to aid in the separation. The vapor from the third stage is liquifled in condenser 9 and the condensate preferably returned to the second stage for further refining. I

The arrangement of the flows between-the various heaters and condensers may be varied to suit the operating conditions. For example, the vapor from the third separator. 8 may becondensed and introduced to the first heater I instead of the second heater 4, or the liquid from the second separator 5 may be introduced to the third heater 1 instead of the first heater I. When there is not much surging in the first heater I, this heater with separator 2 may give excellent quality aminoacetonitrile without further treatment. In this case, the vapor from the first separator 2 is collected as product without further treatment and the vapor from the third separator 8 is con densed and either added to the product or recycled to the first heater I.

Water addition need not be confined to the third heater 1, but may also be added to the first and second heaters I and 2, thus improving their recovery. Normally, however, the improvement in nitrile recovery yield is not justified if the product is to be directly hydrogenated, because of the extra cost of hydrogenating a more dilute nitrile solution. Vacuum is preferably applied to the system at the liquid outlets of the separators and at the exits of the condensers by ordinary means not shown.

When purifying the crude reaction mixture from the amination of formaldehyde cyanhydrin, some ammonia is present, which may, if desired, be separated by evaporation before the mixture is introduced into the purifying units of this invention. The crude reaction mixture, free from solids and containing less than 10% ammonia, is introduced into the system of heaters, separators, and condensers which are maintained at the lowest possible pressure allowing steady flow of materials through the system. For example, it has been found desirable to effect the separation in the first two stages at a pressure of about 20 to about 80mm. and a temperature between about 0., and the separation in the 65 C. and about 85 stainless steel tubular C. under a pressure of approximately 40 mm. provided by any suitable means. From this heater the vapor-liquid mixture is introduced directly into the cyclone separator 2, which is maintained pressure. Approximately 3.06 parts per hour of vapors issue from this-separator, are liquified in condenser 3 and are passedto the second stage of the process togather with 3.19 partsper hour of condensed vapor from condenser 9, wherein they are subjected to substantially the same conditions to which they were subjected in the first stage. The vapors from the second stage are removed at a rate of approximately 5.5 parts per hour, are condensed at 6 and withdrawn from the system as a water-white aqueous solution of aminoacetonitrile. The liquid from separator 5 constitutin about 0.75part per hour is returned to the heater l of the first stage. The liquid from the first stage constituting approximately 2.59 parts per hour are introduced, after the addition of 1 (although from 0.25 to 3 parts may be added if desired) part of water per hour, into heater 1 of the third stage, and from the separator 8 of this stage 3.19 parts per hour of the vapors are withdrawn and returned after condensation at 9 to heater 4 of the second stage. Approximately 0.4 part per hour of liquid is discharged from the third stage and, if desired, may be treated for the small amount of aminoacetonitrile retained therein.

A preferred embodiment of the purification step of the invention is illustrated by this example in which parts are by weight unless otherwise indicated. The crude highly colored reaction mixture, containing about 50% of water and about 50% of aminoacetonitrile and a mixture of contaminating products, obtained by the amination of substantially hyde cyanhydrin and water, is heated to about C.'at atmospheric pressure to drive off most of the-ammonia. The resulting liquid contains about 5% ammonia and is cooled to from 5 to 10 C., filtered and then fed at the rate of about 0.75 foot per minute to the first of three separation stages.

Each heating section consists of a jacketed heater 6 in length and I. D. followed by a 5" I. D. x 8" long cyclone separator. The time of contact in the heaters of each stage is less than 6 minutes and is preferably less than 3 minutes. The vapor from the first stage is condensed and fed to a second stage similar to the first. The liquid from the first stage is fed to a'third stage along with 0.08 lb. of water per pound of the crude nitrile introduced to the refining system. The vapor from the third stage is condensed and fed to the second, while the liquid is run to waste. The vapor from the equimolar weights of formaldeaminoacetonitrile mixt'ure. ,1 .H

2., In a process for, {thefpurification of aminoseem-nam contained in a crude liquid mixture, the stepswhichcomprise passingja crude aqueous a a second stage. is condensed and sent to products storage and the liquid is recycled to the first sep aration stage. The operating conditions are:

l Numerals refer to corresponding separators in the drawing.

The pressure and temperature in the heater of each stage is substantially the same as the respective pressureand temperature in the cyclone separator of that stage. from the second'stage gives an aqueous solution of apure water-white aminoacetonitrile. IRES? much as itis free from tarry. materials, it can be catalytically hydrogenated directly to ethylene diamine in excellent yields and with longcatalyst life. i i

The process 01 the invention may likewise be employed for the preparation of anhydrousv aminoacetonitrile. For example, the crude reaction mixtureobtained by the amination ofiormaldehyde cyanhydrin is passed into a water re-,-

moval column |0,"which is heated by means of the steam-heated ,coittllto distill oif allof the waterand ammonia present. The water-tree product is continuously passed (into the system and 3 subjected to "substantially the same conditionsflor pressure; and temperature used in the treatment. bff aqueous aminoacetonitrile. The flow or crude' anhydrous aminoacetonitrile is the The condensed vapors liquid-vapor mixture into a space of greater volume wherein the vapors and liquids are separated.

4. In a process for the purification ofaminoacetonitrile contained in a crude liquid mixture, the steps which comprise effecting the purification in a plurality of stages, in the first stage passing a relatively small volume of the crude aqueous liquid mixture into a zone heated to a temperature between about 65 to about 95 C.

at a pressure of less than 80 mm., and so constructed that a major portion of the aminoacetonitrile is vaporized within not more than three minutes, and thereafter passing the liquid-vapor mixture into a zone of greater volume wherein the vapors and liquids areseparated, passing the vapors from the first stage into a heating zone and separating zone of the second stage, and

therein subjecting the mixture to substantially the same conditions of temperature and pressure employed in the first stage, passing the liquids from the first stage to a third stage heating zone. wherein this liquid is subjected to a lower pressure than employed in the first stage and to a temperature sufiicient under the pressure superimposed to vaporize a major portion of the a aminoacetonitrile contained therein, returning zone and the liquids from the second stage to the first stage heating zone, whereby substantially all contaminating constituents other than water are removed from the said crude liquid same as described above except that the vapor from separator 5 containing water is sent back to the water removal column Ill instead of being condensed and sent to heater 4. As a result or this treatment, anhydrous aminoacetonitrlle can be obtained not only free from water, but also substantially free from contaminating substances resulting from the formaldehyde cyanhydrin amination reaction or from decomposition of the aminoacetonitrile.

We claim: r

1. In a processior the purification of aminoacetonitrile contained in a crude aqueous liqmixture.

5. In a process for the purification of amino- ,acetonitrile from a mixture thereof dissolved in water containing decomposition products of the aminoacetonitrile and by-products of the formaldehyde ,cyanhydrin-ammonia reaction, the

steps which comprise passing the mixture into a tubular reaction zone. vaporizing therein a major portion of the aminoacetonitrile and water under uid mixture, the steps which comprise heating the crude liquid mixture to a temperature between and 95 C. for not more "than three minutes under a pressure of 5 to 80 mm. until a major portion oi. the aminoacetonltrilehas been vaporized, passing the resulting liquid-vapor mixture into a separating zone and therein separating the vapor from the liquid-vapor liquidmixture into a tubular heating zone, and vaporizing therein a major portion of the aminoacetonitrile under a pressure of from 5 to 80 mm. and a temperature of between about 65 to about 95 C. within not more than three minutes, thereafter passing the liquid-vapor mixture into a space of greater volume wherein the vapors and liquids are separated. a

3. In a process for the purification oi aminoacetonitrile contained in a crude liquid mixture, the steps which comprise passing a crude aqueous liquid mixture through a plurality of heating and a pressure of from 5 to 60 mm. and a temperature of between 65 and 85 C. for not more than three minutes, thereafter passing the resulting liquid-vapor mixture into a zone of greater volume than the heating zone wherein the aminoacetonitrile and water are separated from the unvaporized constituents and thereafter condensing the vaporized aminoacetonitrile.

6. In a process for the purification of aminoacetonitrile contained in a crude aqueous liquid mixture, the steps which comprise passing the crude aqueous liquid mixture under reduced pressure through a tubular heating zone in not more than 3 minutes the zone being maintained at a temperature below 95 C. and suificient to vaporize a major portion of the aminoacetonitrile during its passage through the zone, passing the resulting liquid-vapor mixture into a separating zone andtherein separating the aminoacetonitrile vapor from the liquid-vapor mixture.

'7. The process of claim 6 in which the aminoacetonitrile is subjected in the tubular heating zone to a pressure below millimeters.

ARTHUR G. WEBER. CLARENCE D. BELL.

c (References on following page) 7 8 REFERENCES CITED FOREIGN PATENTS The following references are of record in the Number Country Date file of this patent: 832,259 France June 27, 1938 .6 UNITED STATES PATENTS OTHER REFERENCES Badger and McCabe, Elements of Chemical Number Name I Date Engineering, second edition, published 1936 by 2,274,801 Mills M8123, 1942 McGraw-Hill Book 00., Inc., New York, N. Y., 2,085,679 Gluud et a1 June 29, 1937 1936. (Copy in Library of Congress, pages 177- I 2,054,096 Potts et a1 Sept. 15, 1936 184 

